Aziridine adducts of {60 ,{62 -unsaturated nitriles and polymers thereof

ABSTRACT

This invention relates to a process for pretreating cellulosic fabrics with acid catalysts, and then impregnating said fabrics with aziridine adducts of Alpha , Beta -unsaturated nitriles.

United States Patent Leon H. Chance New Orleans;

George L. Drake, Jr., Metairie, both of La. 8 10,37 1

[72] Inventors App]. No. Filed Mar. 25, 1969 Patented Nov. 2, 1971Assignee IlTeUmtedSEtYi Amerifa as represented by the Secretary ofAgriculture [54] AZIRIDINE ADDUCTS 0F 01,6 -UNSATURATED NITRILES ANDPOLYMERS THEREOF 1 Claim, No Drawings s21u.s.c1 117/56, 3/542, 8/100,8/1 16.2, 117/1395, 1 17/143, 260/2 EN, 260/78.4 N, 260/239 E 51 1111.0..B44dl/092,

[50] Field of Search ..8/54.2, 100, 116.2; 117/56, 139.5 CD, 139.5 A,143 A, 143 R; 260/2 EN, 78.4 N, 239 E Primary Examiner-William D. MartinAssistant Examiner-M. R. Lusignan Attorneys-R. Hoffman and W. BierABSTRACT: This invention relates to a process for pretreating cellulosicfabrics with acid catalysts, and then impregnating said fabrics withaziridine adducts of aJj-unsaturated nitriles.

AZIRIDINE ADDUCTS F afi-UNSATURATED NITRILES AND POLYMERS THEREOF Anonexclusive, irrevocable, royalty-free license in the invention hereindescribed, throughout the world for all purposes of the United StatesGovernment, with the power to grant sublicenses for such purposes, ishereby granted to the Government of the United States of America.

The compounds of the present invention are useful in polymerizing oncotton fabrics to improve their abrasion resistance and receptivity toacid dyes.

The aziridine adducts of afl-unsaturated nitriles of the presentinvention may be prepared by bringing into reactive combination anafi-unsatur'ated nitrile and aziridine. The reaction takes place overv atemperature range, usually about from 60 C. to 80 C. The less reactivenitriles required a catalyst to promote the reaction. Liquid productsare obtained which are purified by distillation.

Compounds related to the compounds of the present invention have beenprepared by techniques known in the art, as shown by H. Bestian, Annalender Chemie 566, 210 (1950), and Yoshida and Naito, J. Chem. Soc. Japan,Ind. Chem. Sect. 55, 455 I952). The prior art, however, does not includethe compounds of the present invention.

Typically illustrative of the apt-unsaturated nitriles employed in theprocess of this invention are: crotonitrile', 2-methyleneglutaronitrile, cinnamonitrile, and methacrylonitrile. Thereaction for the preparation of the compounds of this invention proceedsaccording'to the following equation typified by crotononitrile:

In general, the products prepared by the present invention are formed,as indicated above, by reacting at least one mole of aziridine with onemole of the nitrile. However, an excess of ethylenimine is desirable forobtaining the best yields. The amount of excess aziridine used is notimportant since it may be recovered unchanged upon completion of thereaction.

Reaction can be completed within from about 6 hours to 16 hoursdepending on the temperature and the nitrile utilized. The more reactivenitriles such as crotononitrile and 2- methylene glutaronitrile reactslowly with aziridine at room temperature. After the reaction iscompleted the products are distilled.

Polymers in the form of white powders, brittle solids, or tacky solidscan be formed from the compounds described herein. The polymerizationmay be carried out in aqueous solution, or in organic solvents such asethanol or benzene. The polymerization is promoted by acid catalysts,which may be mineral acids such as hydrochloric, sulfuric or fluoboricacid, organic acids such as acetic acid, or latent acid catalysts suchas zinc fluoborate, zinc nitrate, zinc chloride, zinc sulfate, zincacetate, or magnesium chloride.

The polymers can be deposited on the surface and/or within cotton fiberor cotton fabric, thereby rendering the cotton more susceptible to aciddyes and in some cases more resistant to abrasion. The cotton fiber orfabric may be impregnated with an aqueous solution of the catalyst,dried to remove the water, and then impregnated with a solution of theaziridine adduct of the nitrile. The fabric may be dried at from about25 C. to 100 C.

The following examples illustrate the details of the invention. Theparts given are by weight.

EXAMPLE 1 Preparation of 3-( l-aziridinyl)butyronitrile. Aziridine (50parts) was added dropwise with stirring to a flask containingcmtrmonitrile (67 parts). The solution was heated at reflux for ninehours and the product distilled, yielding 53.7 parts of 3-(l-aziridinyl)butyronitrile, a colorless water soluble liquid, b.p.l94.5-l95.5 C./l65 mm., n,,30 C./0.43979. Anal. calcd. for CoHwNg: C,65.41; H, 9.15; N, 25.43. Found: C, 65.37; H, 9.15; N, 25.44.

EXAMPLE 2 Preparation of 2-( l-aziridinylmethyl)glutaronitrile.Aziridine (30 parts) and 2'-n1ethylene glutaronitrile were mixed in aflask and heated on a water bath at 80 C. for 9.5 hours. The product wasdistilled, yielding 66 parts of 2-(1- aziridinylmethyl)glutaronitrile, acolorless water soluble liquid, b.p. l03-l04C./0:07 mm. anal. calcd, forC l-l N z C, 64.41; H, 7.43; N, 28.17. Found: C, 64.60; H, 7.60; N,28.04.

EXAMPLE 3 Preparation of Aziridine (21.5 parts), cinnamonitrile (53.4parts) and metallic sodium (0.8 parts) were placed in a flask and heatedwith stirring on a water bath at 70 C. for 7 hours. The mixture turnedblack and was viscous. The product was distilled, yielding 29.8 parts of3-(1-aziridinyl)-3-phenyl-propionitrile, a colorless water insolubleoil, b.p. 9l/0.03 mm. Anal. calcd. for C,,H,,N,: C, 76.71; H, 7.02; N,16.27; mol wgt., 172.2. Found: C, 76.88; H, 6.99; N, 16.34; molwgt.,170.

EXAMPLE 4 Preparation of 3-(1-aziridinyl)-2-methylpropionitrile.Aziridine 5 3 parts), methacrylonitrile (67.1 parts) and metallic sodium(0.5 parts) were placed in a flask and heated in a water bath at C. forabout 16 hours. After the first hour of heating about 8 parts of freshaziridine was added, and after 8 hours an additional 8 parts was added.The mixture turned a dark brown and upon distillation yielded 41 partsof 3- (laziridinyl)-2-methylpropionitrile, a colorless water solubleliquid, b.p. 68-70 C./ll mm. Anal. calcd. for C l-1, 19,: C, 65.41; H,9.15; N, 25.43. Found: C, 65.30; H, 9.21; N, 25.44.

EXAMPLE 5 The polymerization of the compounds of examples 1, 2, 3, and 4was carried out in the same manner as described in the following typicalprocedure:

To 3-(1-aziridinyl)2-methylpropionitrile (2.4 parts) in a beaker wasadded with stirring 19 parts of 1 percent aqueous zinc fluoborate. Thesolution turned milky almost immediately and a viscous polymer began toseparate within a few minutes. A white solid also separated with viscousproduct. The viscous portion was soluble in acetone. The solid portionwas a white powder, m.p. 268-69 C. (dec.,), and insoluble in acetone.Anal. found: C, 60.40; H, 8.82; N, 22.96 (based on polymer mixture).

The properties of the other polymers are described in table TABLE 1-Aziridine Adduct Polymer Analysis, 9!: Properties crotononitrile C,63.6l; H, 9.06; Brittle solid,

N,24.49 soluble in acetone cinnamonitrile C,74.92; H, 6.85 Brittle solidN,l5.57 soluble in acetone Z-methylene C, 62.04; H, 7.31; Solid acetoneglutaronitrile N,28.80 (based on insoluble portion,

polymer mixture) and a tacky acetone soluble 70 portion 3-(l-aziridinyl)-3-phenylpropionitrile.

zinc acetate, or magnesium chloride. Ethanol or benzene may be used assolvents for the polymerization instead of water.

EXAMPLE 6 The following example is typical of the treatment of cottonfabric:

A piece of cotton printcloth was impregnated with l percent aqueousZn(BF.) and the excess squeezed out bypassing through pad rolls. Thefabric was dried to remove moisture and then impregnated with a percentaqueous solution of 2- (l-aziridinylmethyl) glutaronitrile, the excesssqueezed out and the fabric again dried. The fabric was then rinsedthoroughly. The polymer weight gain on the fabric was 4.6 percent. Thefabric dyed a darker shade than a control fabric with an acid dye, andhad a flex abrasion resistance (Stoll method) of 813 cycles. This was animprovement over the untreated control fabric, which had a flex abrasionof only 270 cycles.

EXAMPLE 7 A piece of cotton printcloth was treated by exactly the sameprocedure as in example 6 except a 20 percent aqueous solution of3-(1-a2iridiny1)propionitri1e (prepared by reacting acrylonitrile withaziridine) was used. The polymer weight gain on the fabric was 15.8percent. The flex abrasion resistance was 1,125 cycles compared to acontrol fabric at 270 cycles. The sample dyed a darker shade than acontrol fabric with an acid dye.

EXAMPLE 8 A piece of cotton printcloth was treated by exactly the sameprocedure as in example 6 except a 20 percent aqueous solution of3-(1-aziridinyl)butyronitri1e was used. The polymer weight gain on thefabric was 14.4 percent. The flex abrasion was 323 cycles compared to acontrol sample at 270 cycles, The fabric had improved dyeability with anacid dye.

EXAMPLE 9 A piece of cotton printcloth was treated by the same procedurein example 6 except 2 percent aqueous Zn(BF.), was used as a catalystand a 15 percent aqueous emulsion of 3-(1-aziridiny1)-3-phenylpropionitri1e was used. The emulsion contained 1percent dodecyl sodium sulfate as an emulsifying agent. The polymerweight gain on the fabric was 11.3 percent, The fabric had improveddyeability with an acid dye.

We claim:

1. A process for treating cellulosic fabrics to render them moresusceptible to acid dyes which process comprises:

a. padding onto a cellulosic fabric an acid catalyst selected from agroup consisting of hydrochloric acid, sulfuric acid, fluoboric acid,acetic acid, zinc fluoborate, zinc nitrate, zinc chloride, zinc sulfate,zinc acetate, and magnesium chloride,

b. squeezing the fabric free of excess catalyst,

c. drying the fabric,

d. impregnating on the fabric an aziridine adduct selected from a groupconsisting of 3-(1-aziridiny1)butyro-nitri1e, 2-(l-aziridinylmethyl)glutaronitrile, 3-( l-aziridinyl)-3-phenylpropionitrile, and 3-(l-aziridinyl)-2-methy1- propionitrile,

e. drying the impregnated fabric,

f. washing the fabric free of excess reagents.

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